CN112876783B - High-strength plastic sole material and preparation method thereof - Google Patents

High-strength plastic sole material and preparation method thereof Download PDF

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CN112876783B
CN112876783B CN202110060562.5A CN202110060562A CN112876783B CN 112876783 B CN112876783 B CN 112876783B CN 202110060562 A CN202110060562 A CN 202110060562A CN 112876783 B CN112876783 B CN 112876783B
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foaming
agent
graphene oxide
heating
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CN112876783A (en
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朱江
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Jiangxi Zhengbo Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

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  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to the technical field of shoemaking, and provides a high-strength plastic sole material and a preparation method thereof. Wherein the plastic sole material comprises: 80-100 parts of PVC resin, 20-40 parts of chlorinated polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer EVA, 5-20 parts of composite modified nano graphene oxide material, 5-20 parts of thermoplastic elastomer, 5-20 parts of naphthenic oil and 1-6 parts of foaming agent. Through nano SiO 2 TiO 2 nanoparticles 2 And the composite modified nano graphene oxide material modified by the silica micropowder improves the internal bonding force of the plastic sole material and improves the comprehensive performance of the material, and the sole material prepared by the foaming process is of a porous foaming structure, so that the obtained sole has the advantages of light weight, wear resistance, high toughness, high strength and strong shock absorption performance.

Description

High-strength plastic sole material and preparation method thereof
Technical Field
The invention relates to the technical field of shoemaking, in particular to a high-strength plastic sole material and a preparation method thereof.
Background
The sole is rather complex in construction and in a broad sense may include all of the materials forming the sole, such as the outsole, midsole and heel. In a narrow sense, only the outsole is referred to, and the common characteristics of the general sole materials should have the characteristics of wear resistance, water resistance, oil resistance, heat resistance, pressure resistance, impact resistance, good elasticity, easy adaptation to the foot shape, difficult deformation after shaping, heat preservation, easy moisture absorption and the like, and simultaneously should be matched with the midsole to have the brake function of preventing slipping and easy stopping when the foot is changed during walking.
The PVC sole has good physical properties and chemical properties. It is a plastic material from the visual point of view, and is characterized by light weight, strong glossiness, but lack of texture. PVC is a polar non-crystalline high polymer, has stronger acting force among molecules, and is a hard and brittle material; the impact strength is low. After the impact modifier is added, the elastomer particles of the impact modifier can reduce the stress caused by the total crazing, prevent the crazing from expanding and growing by utilizing the deformation and shear band of the particles, and absorb the impact energy transmitted into the material body, thereby achieving the aim of impact resistance. However, due to insufficient wear resistance and poor tensile property of PVC materials, shoes are prone to aging, yellowing, hardening, brittle fracture and the like in a strong sunlight or high temperature environment, which greatly affects the use environment and consumption range of the shoes.
With the upgrading of industrial technologies, plastic products are no longer on low-end performance requirements. The higher quality plastic material can meet the requirements of people on high strength, light weight and high stability. However, the quality of the product cannot be effectively improved due to the limitation of the inherent properties of the rubber material. The shoe-making field is obvious, and the plastic has poor air permeability, thickness and poor wear resistance, thereby seriously influencing the comfort and the service life of the plastic shoes.
Disclosure of Invention
Therefore, the use of plastics as sole processing materials requires performance improvement to improve the comfort and the service life, which is of great significance to the superior performance and environmental protection of plastics in the field of shoe making. The present invention is to overcome at least one of the above disadvantages and drawbacks of the prior art, and to provide a high strength plastic sole material and a method for preparing the same.
The invention aims at providing a high-strength plastic sole material which comprises the following raw materials in parts by weight: 80-100 parts of PVC resin, 20-40 parts of chlorinated polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer EVA, 5-20 parts of composite modified nano graphene oxide material, 5-20 parts of thermoplastic elastomer, 5-20 parts of naphthenic oil and 1-6 parts of foaming agent.
Preferably, the composite modified nano-graphene material comprises the following raw materials in parts by weight: nano SiO 2 2 5 to 10 portions of nano TiO 2 5-10 parts of silicon powder, 5-10 parts of silicon micropowder and 5-10 parts of graphene oxide.
Preferably, the thermoplastic elastomer is SEBS and/or SBS, and has excellent performances of high elasticity, aging resistance, oil resistance and convenience in processing; the foaming agent is azodicarbonamide AC, and the content of the residual quantity of the foaming agent in the product is greatly reduced compared with that of a common foaming product, so that the product is more environment-friendly.
Preferably, the foaming agent also comprises 0.2-2 parts of foaming auxiliary agent, wherein the foaming auxiliary agent is zinc oxide ZnO and/or zinc stearate ZnSt. The foaming auxiliary agent is added, so that the foaming temperature is reduced, the melt strength of the polyethylene in the foaming tool is improved, the phenomena of fracture and breakage are reduced, and the yield is improved.
In another aspect of the present invention, a method for preparing a high strength plastic sole material is provided, which comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 TiO 2 nanoparticles 2 Adding the silicon micro powder, the dispersing agent, the defoaming agent and the wetting agent into deionized water, and stirring and dispersing for a period of time to obtain emulsion;
s12, preparing ethanol water solution of trimethylolpropane with the mass concentration of 10-20%, adding graphene oxide, a surfactant, a coupling agent and a modification treatment agent, and uniformly mixing to obtain mixed solution;
s13, adding the emulsion into the mixed solution, carrying out heating ultrasonic treatment or heating stirring treatment, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain elastomer mother liquor;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the materials, and transferring the materials into a foaming tool for foaming;
and S5, cooling to 80-120 ℃ after foaming is finished, placing the mixture into a mold, pressurizing and preserving heat for a period of time, and then cooling to room temperature to obtain the high-strength plastic sole material.
Preferably, the dispersant in step S11 is one or more of dispower 929, EFKA SL 3034, dow Corning 51; the defoaming agent is one or more of Deform 6800, efka SL 2038, SRE-CN and Dow Corning 65; the wetting agent is one or more of alkyl sulfate, sulfonate and phosphate;
in the step S12, the surfactant is one or more of sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate and ammonium fatty alcohol polyoxyethylene ether sulfate; the coupling agent is one or more of dodecyl silane, aminopropyl triethoxysilane and titanate coupling agent; the modifying and treating agent is one or more of hexamethyl-dinitrogen silicane, dimethyl dichlorosilane and dimethyl silicone.
Preferably, the conditions of the heating ultrasound in step S13 are: the heating temperature is 50-90 ℃, and the ultrasonic frequency is 50-100 kHz; the heating and stirring conditions are as follows: the heating temperature is 50-90 ℃, and the stirring speed is 1000-1500 r/min.
Preferably, the heating and mixing temperature in the step S3 is 50-80 ℃, and the time is 10-60 min.
Preferably, the foaming temperature in step S4 is 150-180 ℃, and the foaming time is 10-20 min.
Preferably, the pressure of the pressure and heat preservation treatment in the step S5 is 1.2-2.0 MPa, and the time is 30-60 min.
The invention can obtain the following beneficial effects:
1. the composite modified nano graphene oxide material provided by the invention is used for modifying a PVC material, so that the aging resistance and the wear resistance of the PVC material are improved, and the nano SiO 2 And nano TiO 2 The antibacterial property, the aging resistance and the temperature resistance of the material are synergistically improved, the wear resistance of the sole is improved by the silica powder, and the high-strength plastic sole material is prepared. According to the invention, the composite modified nano graphene oxide material is added into the plastic material in a co-foaming manner and combined with a plastic interface, and the graphene oxide material and the plastic material are mixed and interwoven to form a complex mesh structure, so that the internal bonding force of the plastic sole material is improved, the comprehensive performance of the material is improved, the sole material prepared by a foaming process is of a porous foaming structure, and the obtained sole material is of a porous foaming structureThe sole has the advantages of light weight, wear resistance, high toughness, high strength and strong shock absorption performance. In the foaming process, the low-hardness elastomer is obtained by utilizing the thermoplastic elastomer and the naphthenic oil, the material obtained by foaming has lower hardness, good elasticity and high toughness, and the toughness, the temperature resistance and the aging resistance of the obtained sole material are further improved.
2. According to the invention, by adding the composite modified nano graphene oxide material, the pollution resistance to inorganic substances such as water, dust and the like is greatly improved, the waterproof and dirt-resistant effects of the plastic sole material are improved, and the plastic sole material is convenient to clean.
3. The composite modified nano graphene oxide material and nano TiO are prepared by the method 2 Nano SiO 2 The modified silicon micro powder is filled and grafted on the graphene oxide, so that the obtained material is high in surface activity and structural strength, and the compatibility of the modified silicon micro powder with other plastic raw materials can be greatly improved through modification, and the modified silicon micro powder is favorable for foaming in combination with a plastic interface. In addition, through modification, the toughness and the wear resistance of the plastic sole material are greatly improved.
4. The sole material disclosed by the invention is high in mechanical strength, excellent in impact resistance, higher in elastic recovery capability, more resistant to dirt, and capable of adapting to operation in a complex environment, and the service life of the plastic sole is prolonged.
5. The preparation method of the plastic sole material has high processing technology stability and can be applied to industrial large-scale production.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The equipment and raw materials used in the preferred embodiment of the invention are commercially available.
Example 1:
high-strength plastic sole materialThe feed comprises the following raw materials in parts by weight: 80 parts of PVC resin, 20 parts of chlorinated polyethylene, 30 parts of ethylene-vinyl acetate copolymer EVA, 20 parts of composite modified nano graphene oxide material, 10 parts of thermoplastic elastomer SBS, 10 parts of SEBS, 5 parts of naphthenic oil and 1.5 parts of azodicarbonamide AC foaming agent. The composite modified nano graphene material comprises the following raw materials in parts by weight: nano SiO 2 5 parts of nano TiO 2 5 parts of silicon powder, 5 parts of graphene oxide, 10 parts of surfactant and 2 parts of coupling agent.
A preparation method of a high-strength plastic sole material comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 TiO 2 nanoparticles 2 Adding the silicon micro powder, a dispersing agent Disponer 929, a defoaming agent Deform 6800 and a wetting agent sodium alkyl sulfate into deionized water, and stirring and dispersing for a period of time to obtain an emulsion with the total mass concentration of 2.25%;
s12, preparing ethanol water solution of trimethylolpropane with the mass concentration of 10%, adding graphene oxide, surfactant lauryl sodium sulfate, coupling agent dodecyl silane and modification treatment agent hexamethyl-dinitrogen silane, and uniformly mixing to obtain mixed solution;
s13, adding the emulsion into the mixed solution, heating and stirring at 50 ℃ for 90min at the speed of 1000r/min, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain elastomer mother liquor, wherein the heating and mixing temperature is 50 ℃ and the time is 60min;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the elastomer mother liquor, transferring the elastomer mother liquor into a foaming tool to foam, wherein the foaming temperature is 150 ℃, and the foaming time is 20min;
and S5, cooling to 80 ℃ after foaming is finished, placing the mixture into a mold for pressurization and heat preservation treatment for a period of time, wherein the pressure of the pressurization and heat preservation treatment is 1.2MPa, and the time is 60min, and then cooling to room temperature to obtain the high-strength plastic sole material.
Example 2:
a high-strength plastic sole material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 40 parts of chlorinated polyethylene, 10 parts of ethylene-vinyl acetate copolymer EVA, 5 parts of composite modified nano graphene oxide material, 5 parts of thermoplastic elastomer SBS, 20 parts of naphthenic oil, 6 parts of azodicarbonamide AC foaming agent and 0.2 part of zinc oxide ZnO foaming auxiliary agent. The composite modified nano graphene material comprises the following raw materials in parts by weight: nano SiO 2 2 10 portions of nano TiO 2 10 parts of silicon powder, 10 parts of graphene oxide, 5 parts of surfactant and 5 parts of coupling agent.
A preparation method of a high-strength plastic sole material comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 TiO 2 nanoparticles 2 Adding silicon micro powder, a dispersing agent EFKA SL 3034, a defoaming agent Efka SL 2038 and wetting agent sodium sulfonate into deionized water, and stirring and dispersing for a period of time to obtain an emulsion with the total mass concentration of 2.5%;
s12, preparing an ethanol water solution of trimethylolpropane with the mass concentration of 20%, adding graphene oxide, a surfactant, a coupling agent and a modification treatment agent, and uniformly mixing to obtain a mixed solution;
s13, adding the emulsion into the mixed solution, heating and stirring at 90 ℃ for 30min at a speed of 1500r/min, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain elastomer mother liquor, wherein the heating and mixing temperature is 80 ℃, and the time is 10min;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the elastomer mother liquor and the elastomer mother liquor, and transferring the elastomer mother liquor into a foaming tool for foaming, wherein the foaming temperature is 180 ℃, and the foaming time is 10min;
and S5, cooling to 120 ℃ after foaming is finished, placing the mixture into a mold, performing pressure and heat preservation treatment for a period of time, wherein the pressure of the pressure and heat preservation treatment is 2.0MPa, and the time is 30min, and then cooling to room temperature to obtain the high-strength plastic sole material.
Example 3:
a high-strength plastic sole material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 30 parts of chlorinated polyethylene, 20 parts of ethylene-vinyl acetate copolymer EVA, 10 parts of composite modified nano graphene oxide material, 10 parts of thermoplastic elastomer SEBS, 10 parts of naphthenic oil, 4 parts of azodicarbonamide AC foaming agent and 1 part of zinc stearate ZnSt foaming auxiliary agent. The composite modified nano graphene material comprises the following raw materials in parts by weight: nano SiO 2 8 parts of nano TiO 2 8 parts of silicon powder, 8 parts of graphene oxide, 4 parts of surfactant and 3 parts of coupling agent.
A preparation method of a high-strength plastic sole material comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 TiO 2 nanoparticles 2 Adding the silicon micro powder, a dispersing agent Dow Corning 51, a defoaming agent SRE-CN and a wetting agent alkyl sulfate into deionized water, and stirring and dispersing for a period of time to obtain an emulsion with the total mass concentration of 2.25%;
s12, preparing 15% trimethylolpropane ethanol aqueous solution, adding graphene oxide, surfactant lauryl sodium sulfate, coupling agent titanate coupling agent and modification treatment agent dimethyl silicone, and uniformly mixing to obtain a mixed solution;
s13, adding the emulsion into the mixed solution, heating and ultrasonically treating for 30min at 75 ℃ and an ultrasonic frequency of 80kHz, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain elastomer mother liquor, wherein the heating and mixing temperature is 60 ℃ and the time is 45min;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the elastomer mother liquor, transferring the elastomer mother liquor into a foaming tool to foam, wherein the foaming temperature is 160 ℃, and the foaming time is 15min;
and S5, cooling to 110 ℃ after foaming is finished, placing the mixture into a mold for pressurization and heat preservation treatment for a period of time, wherein the pressure of the pressurization and heat preservation treatment is 1.5MPa, and the time is 50min, and then cooling to room temperature to obtain the high-strength plastic sole material.
Example 4:
a high-strength plastic sole material comprises the following raw materials in parts by weight: 90 parts of PVC resin, 35 parts of chlorinated polyethylene, 22 parts of ethylene-vinyl acetate copolymer EVA, 15 parts of composite modified nano graphene oxide material, 6 parts of thermoplastic elastomer SEBS, 12 parts of SBS, 12 parts of naphthenic oil, 3 parts of azodicarbonamide AC foaming agent, 0.5 part of zinc oxide ZnO foaming auxiliary agent and 0.8 part of zinc stearate ZnSt foaming auxiliary agent. The composite modified nano graphene material comprises the following raw materials in parts by weight: nano SiO 2 2 6 parts of nano TiO 2 8 parts of silicon powder, 6 parts of silicon micropowder, 9 parts of graphene oxide, 3 parts of surfactant and 2.5 parts of coupling agent.
A preparation method of a high-strength plastic sole material comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 TiO 2 nanoparticles 2 Adding silicon powder, dispersing agents Disponer 929, EFKA SL 3034, a defoaming agent Dow Corning 65, a wetting agent alkyl sulfate and triethyl phosphate into deionized water, and stirring and dispersing for a period of time to obtain an emulsion with the total mass concentration of 2.0%;
s12, preparing an ethanol aqueous solution of trimethylolpropane with the mass concentration of 18%, adding graphene oxide, surfactant lauryl sodium sulfate, fatty alcohol-polyoxyethylene ether ammonium sulfate, coupling agent dodecylsilane, titanate coupling agent, modifying treatment agent hexamethyl-dinitrogen silane and dimethyl silicone, and uniformly mixing to obtain a mixed solution;
s13, adding the emulsion into the mixed solution, heating and ultrasonically treating for 40min at the temperature of 80 ℃ and the ultrasonic frequency of 60kHz, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain elastomer mother liquor, wherein the heating and mixing temperature is 70 ℃, and the time is 30min;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the elastomer mother liquor, transferring the elastomer mother liquor into a foaming tool to foam, wherein the foaming temperature is 170 ℃, and the foaming time is 13min;
and S5, cooling to 100 ℃ after foaming is finished, placing the mixture into a mold for pressurization and heat preservation treatment for a period of time, wherein the pressure of the pressurization and heat preservation treatment is 1.8MPa, and the time is 40min, and then cooling to room temperature to obtain the high-strength plastic sole material.
Comparative example 1:
the rest of the process is the same as example 4 without adding the composite modified nano graphene oxide material.
Comparative example 2:
the same procedure as in example 4 was repeated except that only graphene oxide was added without modification.
Comparative example 3:
the silica fume was removed, and the same procedure as in example 4 was repeated.
Comparative example 4:
the thermoplastic elastomer SEBS was replaced by the polyolefin elastomer POE, and the remaining process parameters were the same as in example 4.
TABLE 1
Figure BDA0002902191060000091
Figure BDA0002902191060000101
As can be seen from the data in Table 1, the impact resistance, stretchability, temperature resistance, wear resistance and elasticity of the PVC plastic sole material are greatly improved by adding the composite modified nano graphene oxide material (comparative example 1), and the graphene oxide material is processed by nano SiO 2 TiO 2 nanoparticles 2 After the silicon micropowder is modified (comparative example 2), compared with the method of only adding graphene oxide, the impact resistance, stretchability, temperature resistance, wear resistance and elasticity of the plastic sole material are further improved; the silicon micropowder is used for modifying the graphene oxide material (comparative example 3), so that the impact resistance, the temperature resistance and the wear resistance of the plastic sole material are improved; the thermoplastic elastomer (comparative example 4) has a great influence on the stretchability, temperature resistance and elasticity of the plastic sole material. In conclusion, the plastic sole prepared by the invention has good elasticity, temperature resistance and wear resistance, and good mechanical property, and the service life of the plastic shoe is prolonged.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still make modifications to the technical solutions described in the foregoing embodiments, or make equivalent substitutions and improvements to part of the technical features of the foregoing embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. The high-strength plastic sole material is characterized by comprising the following raw materials in parts by weight: 80-100 parts of PVC resin, 20-40 parts of chlorinated polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer EVA, 5-20 parts of composite modified nano graphene oxide material, 5-20 parts of thermoplastic elastomer, 5-20 parts of naphthenic oil and 1-6 parts of foaming agent;
the thermoplastic elastomer is SEBS and/or SBS, and the foaming agent is azodicarbonamide AC;
the foaming agent also comprises 0.2-2 parts of foaming auxiliary agent, wherein the foaming auxiliary agent is zinc oxide ZnO and/or zinc stearate ZnSt;
the preparation method of the high-strength plastic sole material comprises the following steps:
s1, preparing a composite modified nano graphene oxide material:
s11, taking nano SiO 2 Nano TiO 2 2 Adding the silicon micro powder, the dispersing agent, the defoaming agent and the wetting agent into deionized water, and stirring and dispersing for a period of time to obtain emulsion;
s12, preparing ethanol water solution of trimethylolpropane with the mass concentration of 10-20%, adding graphene oxide, a surfactant, a coupling agent and a modification treatment agent, and uniformly mixing to obtain mixed solution;
s13, adding the emulsion into the mixed solution, carrying out heating ultrasonic treatment or heating stirring treatment, separating to obtain a solid product, and drying to obtain the product;
s2, mixing the thermoplastic elastomer with naphthenic oil to obtain a low-hardness elastomer;
s3, heating and mixing the low-hardness elastomer, the PVC resin, the chlorinated polyethylene, the ethylene-vinyl acetate copolymer EVA and the foaming agent to obtain an elastomer mother solution;
s4, adding the composite modified nano graphene oxide material into the obtained elastomer mother liquor, continuously heating and mixing for a period of time to uniformly mix the materials, and transferring the materials into a foaming tool for foaming;
s5, cooling to 80-120 ℃ after foaming is finished, placing the mixture into a mold for pressurizing and heat preserving treatment for a period of time, and then cooling to room temperature to obtain the high-strength plastic sole material;
in the step S11, the dispersing agent is one or more of Disponer 929, EFKA SL 3034 and Dow Corning 51; the defoaming agent is one or more of Deform 6800, efka SL 2038, SRE-CN and Dow Corning 65; the wetting agent is one or more of alkyl sulfate, sulfonate and phosphate;
in the step S12, the surfactant is one or more of sodium dodecyl sulfate, ammonium dodecyl sulfate, fatty alcohol-polyoxyethylene ether sodium sulfate and fatty alcohol-polyoxyethylene ether ammonium sulfate; the coupling agent is one or more of dodecyl silane, aminopropyl triethoxysilane and titanate coupling agent; the modifying treatment agent is one or more of hexamethyl-dinitrogen silane, dimethyl dichlorosilane and dimethyl silicone;
the conditions of the heating ultrasound in the step S13 are as follows: the heating temperature is 50-90 ℃, and the ultrasonic frequency is 50-100 kHz; the heating and stirring conditions are as follows: the heating temperature is 50-90 ℃, and the stirring speed is 1000-1500 r/min;
the heating and mixing temperature in the step S3 is 50-80 ℃, and the time is 10-60 min;
in the step S4, the foaming temperature is 150-180 ℃, and the foaming time is 10-20 min;
the pressure of the pressurization and heat preservation treatment in the step S5 is 1.2-2.0 MPa, and the time is 30-60 min;
the composite modified nano graphene material comprises the following raw materials in parts by weight: nano SiO 2 5 to 10 portions of nano TiO 2 5-10 parts of silicon powder, 5-10 parts of silicon micropowder and 5-10 parts of graphene oxide.
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